Alkoxy-substituted group 6 allenylidene complexes – Synthesis and properties

Zitieren

Dateien zu dieser Ressource

Dateien Größe Format Anzeige

Zu diesem Dokument gibt es keine Dateien.

SZESNI, Normen, Bernhard WEIBERT, Helmut FISCHER, 2006. Alkoxy-substituted group 6 allenylidene complexes – Synthesis and properties. In: Inorganica Chimica Acta. 359(2), pp. 617-632. ISSN 0020-1693. Available under: doi: 10.1016/j.ica.2005.08.010

@article{Szesni2006Alkox-22886, title={Alkoxy-substituted group 6 allenylidene complexes – Synthesis and properties}, year={2006}, doi={10.1016/j.ica.2005.08.010}, number={2}, volume={359}, issn={0020-1693}, journal={Inorganica Chimica Acta}, pages={617--632}, author={Szesni, Normen and Weibert, Bernhard and Fischer, Helmut} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/22886"> <dcterms:issued>2006</dcterms:issued> <dc:rights>deposit-license</dc:rights> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-31T16:34:18Z</dcterms:available> <dc:creator>Szesni, Normen</dc:creator> <dc:contributor>Szesni, Normen</dc:contributor> <dcterms:abstract xml:lang="eng">Bis(alkoxy)allenylidene complexes, [(CO)5Mdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OR′)OR], as well as mono(alkoxy)allenylidene complexes, [(CO)5Mdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OR′)Ph], of chromium and tungsten are accessible from propynones [Hsingle bondCtriple bond; length of mdashCsingle bondC(double bond; length as m-dashO)Ph] or propynoic acid esters [Hsingle bondCtriple bond; length of mdashCsingle bondC(double bond; length as m-dashO)OR; R = Et, (−)-menthyl, endo-bornyl] by the following reaction sequence: (a) deprotonation of the alkynes, (b) reaction with [(CO)5M-THF] (M = Cr, W), and (c) alkylation of the resulting alkynyl metallate, [(CO)5Msingle bondCtriple bond; length of mdashCsingle bondC(double bond; length as m-dashO)R], with Meerwein salts. Vinylidene complexes, [(CO)5Mdouble bond; length as m-dashCdouble bond; length as m-dashC(R′)C(double bond; length as m-dashO)OR], are formed as a by-product by Cβ-alkylation of the alkynyl metallate. Dimethylamine displaces one alkoxy substituent of the bis(alkoxy)allenylidene complexes to give dimethylamino(alkoxy)allenylidene complexes, [(CO)5Mdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OR)NMe2]. The analogous reaction of dimethylamine with a mono(alkoxy)-substituted allenylidene complex affords the aminoallenylidene complex [(CO)5Crdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(NMe2)Ph]. When the amine is used in large excess, the α,β-unsaturated aminocarbene complex [(CO)5Crdouble bond; length as m-dashC(NMe2)single bondC(H)double bond; length as m-dashC(NMe2)Ph] is additionally formed by addition of the amine across the Cαsingle bondCβ-bond of the allenylidene ligand. The reaction of [(CO)5Mdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OEt)2] with dimethyl ethylenediamine offers access to bis(amino)allenylidene complexes, in which Cγ is part of a five-membered heterocycle. Photolysis of bis(alkoxy)allenylidene complexes in the presence of triphenylphosphine yields tetracarbonyl- and tricarbonyl{bis(phosphine)}allenylidene complexes. Diethylaminopropyne inserts into the Cβdouble bond; length as m-dashCγ bond of [(CO)5Mdouble bond; length as m-dashCdouble bond; length as m-dashCdouble bond; length as m-dashC(OEt)OMethyl] to give alkenylallenylidene complexes. Subsequent acid-catalyzed intramolecular cyclization affords a pyranylidene complex.</dcterms:abstract> <dc:contributor>Weibert, Bernhard</dc:contributor> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dcterms:title>Alkoxy-substituted group 6 allenylidene complexes – Synthesis and properties</dcterms:title> <dc:creator>Weibert, Bernhard</dc:creator> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:language>eng</dc:language> <dc:contributor>Fischer, Helmut</dc:contributor> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/22886"/> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-05-31T16:34:18Z</dc:date> <dcterms:bibliographicCitation>Inorganica Chimica Acta ; 359 (2006), 2. - S. 617-632</dcterms:bibliographicCitation> <dc:creator>Fischer, Helmut</dc:creator> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> </rdf:Description> </rdf:RDF>

Das Dokument erscheint in:

KOPS Suche


Stöbern

Mein Benutzerkonto